Lubricating grease composition



2 Sheets-Sheet l J. C. ZIMMER lET AL Filed Oct. 24, 1941 July 31, 1945.

LUBRICATING GREASE COMPOSITION AJuly 31, 1945. J. c. ZIMMER ET AL 2,380,893

LUBRICATING GREASE COMPOSITION Filed Oct. 24, 1941 2 Shets-Sheet, 2

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L 2/ 2O Z4 .scrmbszz CH/L L En Patented July 31, 1945 LUBRICATING GREASE COMPOSITION` John C. Zimmer, Union. and Arnold J. Monroy, Clark Township, Union County, N. J., assignors to Standard Oil Development Company, a corporation of Delaware Application October 24, 1941, Serial No. 416,313

In Canada November 15,1937

1c claims.

This invention relates to compositions adapted for the lubrication of machinery operated under conditions of local high temperature increases, of irregular and shock load effects or where the machinery is exposed to a muddy or water-y drenching environment. and where frictional forces beyond the nlm strength oi' any hydrocarbon lubricating oil base material are frequently encountered. The invention relates more specilically to semiiluid grease compositions containing aluminum stearate as the main soap constituent adapted for the lubrication of chassis parts of automobiles and crawler-type tractors. The present application is a continuation-in-part of our copending application Serial No. 255,452 iiled on February 9, 1939, now Patent No. 2,264,- 353 and also is related in subject matter to our copending application, Serial No. 416,314 also tiled on October 24, i941.-

For the lubrication of machinery for which compositions of this invention are adapted, the illustration of the satisfactory operation of a typical track roller may be taken. The lubricant in that case is forced under pressure into the main roller mechanism through the hollow shaft and the composition has to flow largely under its own weight during operation from this supply to the bearing parts of the mechanism, otherwise inaccessible to the composition. Also, a quantity of lubricant in excess of that normally required for lubrication is required to be forced into the track roller mechanism to expel from the main bearing parts the old lubricant in order to remove accumulations of dirt and dust which, when compacted with the used grease. increase friction and cause local heating eiects.

in! submerged in a muddy or water-drenching environment: having the capacity pf being suiilciently. mobile to be handled and dispensed at normal atmospheric temperatures from grease guns ordinarily available at commercial outlets; and consistency to be able to flow under its own weight but yet notI fluid enough to leak out or 'be splattered from the machinery parts under operating conditions. An added characteristic of a suitable lubricating grease for such type machinery is that the composition must preferen-A these conditions a persistently heavy iilm of lu-l bricating properties which will also act as a seal against vthe entrance of water and dirt to the bearing surfaces during operating conditions. y

Criteria of quality of grease compositions are specic ranges in value of consistency as indicated by the work penetration test (A. S. T. M. D217, 33T) and the S. I. L. Mobilometer (Ind.Eng. Chem. An Ed. May 15, 1940, pages 285-7), of body density, of adhesiveness to metallic surfaces, of internal cohesion and of melting points. These characteristics depend upon the phsyical and chemical relationships of the ingredients in the composite and the reaction of the composite to the effects of'speed, pressure and heat during service. I n many commercial greases a relationship between the various constituents is desirably attained so that a composite is formed consisting of a minor portion of a colloidal dispersion of metal soaps in a relatively stable emulsion of a major portion of a colloidal dispersion of other anddifferent type metal soaps in a mineral oil of suitable consistency. It is considered particularly important that the colloidal phase be relatively stable and form a satisfactorily adhesive lubricating nlm on the bearing surfaces and that the colloidal phase oiler substantial resistance toward heat conduction from the surface iilm into the mass so asto minimize the eifect of friction, speed and load during service upon the bulk of the grease composition.

The present invention relates particularly to stabilized aluminum soapsrease compositions,

containing aluminum stearate as the main metal soap ingredient. It has been known for some time that when aluminum stearate in an amount v of about 8% by weight is admixed and heated with a mineral oil and the mass cooled, the desirable transition in structure of th'e mass, from being a stringy liquid to a consistency of a relatively solid gel, does not usually satisfactorily occur. The cause of the failure has not been definitely determined, but it would seem from photomicrographs to be due to a recrystallization of the aluminum stearate at a temperature below about 150 F. If the mineral oil-aluminum stearate mixture is rapidly cooled to a temperature of about 150 F. or below, the aluminum stearate crystallizes and there is obtained a mixture of oil and coarsely dispersed soap granules. Inour copending ap- -plication, Serial No. 255,542 now Patent No. 2,264,353, it was disclosed that by adding to the aluminum stearate about 10% by weight of either aluminum naphthenate or aluminum oleate admixed with' about 20% free stearic acid, this difilculty was overcome and a lower transition temperature was obtained upon the composite than upon a mixture having the same metal soap content but consistng of aluminum stearate only. It was also disclosed that many commercial supplies of aluminum stearate vary in the percentage of free acidity from about 5% to 15% but that such free acidity was insufficient to have the desired lowering effect upon the transition temperature and to have the stabilizing effect during storage upon consistency. Thus, many processing diniculties in the manufacture of aluminum soap greases were overcome by adding to the aluminum stearate small quantities of either aluminum naphthenate or aluminum oleate.

In the prior art the cooling from 140 F. to 160 F. to permit the transition from the liquid to the gel structure was usually effected by pouring the hot liquid mixture from the heating equipment into shallow pans holding between about 50 and 100 pounds and having a depth -of several inches and allowing th'e mass to cool overnight. The cooled mass from this pan cooling, as it is termed. was then passed to settling equipment which was usually the kettle equipment in which the mixture was previously heated, then stirred or reworked, at it is commonly termed, to develop a uniform consistency, and filtered into containers. This slow pan cooling and reworking procedure was found to be the only satisfactory method of cooling the grease mixture to eect the desired transition in structure and developing therein a desirable consistency. In other type cooling stearic acid to the grease mixture improved the stability of the composition during storage especially 'as regards the development of increased consistency.

It has now been found that compounds other th'an aluminum naphthenate and aluminum oleate admixed with free stearic acid have the ability to lower the transition temperature of aluminum stearato-mineral oil mixtures and that acids other than stearic acid improve the stability of aluminum soap grease compositions during storage. The newly discovered effective compounds are naphthenic acids and fatty acids in general containing between about 10 and 20 carbon atoms in the molecule, especially oleic acid, in amounts of about 10% by weight of the aluminum stearato. l It hasbeen found th'at with these compounds the total soap admixture to the oil may be reduced and that the 'transition temperature of the composite may be reduced from the temperature range-of between 150 F. and 160 F. for mineral oil-aluminum stearate mixtures to l between ,110 F. and 120 F. and even as low as equipment, such as the shipping containers, the

grease mixture after cooling to atmospheric temperatures is found Ato be of a heterogeneous character, the center being a relatively liquid oil,` while the outer portion is relatively hard, and upon reworking a uniform desirable consistency is seldom obtained.

The prior art procedures for preparing alumibetween 90 F. and ,100 F. when the naphthenic acids Aare employed. Furthermore, the grease compositions containing aluminum naphthenate or aluminum oleate, or oleic acid or naph'thenic acids in amounts of about 10% by weight of the stearato can be quickly cooled to the temperature at which transition occurs without any substantial recrystallization or partial recrystallization of the aluminum stearate and there is obtained after such cooling. a smooth,unctuous product l having no grainy structure.

In this regard, attention is directed to Figure 1. In Figurel 1 there is presented a series of curves showing the effect of maintaining at relatively constant atmospheric conditions various grease compositions containing aluminum stearate in an amount of '7% lby weight relative to the mineral oil as obtained by plotting worked penetration data and time in hours. Comparison between four of the curves, namelyvA, B, C and H shows that a grease mixture containing 0.7% aluminum naphthenate and 1% oleic acidY in addition to the 7% aluminum stearate blended in the oil can after heating be cooled very satisfactorily to a temperature of 116 F. to effect the desirable structural transition to a gel, whereas in the absence of these compounds an aluminum stearatemineral oil grease of less satisfactory consistency is obtained by cooling to 156 F. and very unsatisfactory compositions are obtained by cooling Wto temperatures of 148 F. and 140 F. Comparison of the four curves C, D, E and F shows that the impurities associated with the aluminum stearate in commercial supplies determine for the composition the transition temperature and instability as regards consistency during storage. Comparison of curves G and H shows that the extent of the effect of aluminum naphthenate and oleic acid upon the transition temperature of aluminum stearate is dependent upon the impurities associated with the aluminum stearato but that otherwise the eiect upon aluminum stearate in mineral oil is substantially the same as indicated by the related consistency values for both compositions after ten hours storage.

The further`eiects of the newly discovered active compounds in blending with aluminum stearate in mineral oil to give greases of desirable highly stabilized consistencies containing lower soap contents and of permitting rapid cool- 4 i' l a'aaoas ing to 'the lowery transition temperatures, are

shown by theiollowing tabulation ot data:

at' ateniperatureibetween 'about 280 F. and 3.50""11..y

Soap Composition Transition Worked P t peegra Remarks ercen o content 'lype .lemp. Time F. Houra 9.0 Commercial aluminum stearato, Cr, only 145-160 .8-12 330 Satisfactory (pen cooling). 7.o .do 145-160 350-370 Greiny duid unsatisfactory if uick chilled below thexedtranbsition tami realite bu iiiheldtiasndlowly coo coo e ease ssa ac 1.1 my commercial aluminum sama, c., +109:J ne zo aso setmwwryp n? g' 'y auminum na hthenate. f 6.6 907 commercie aluminum stearato, C4, +10% 115 12 340 Do.

auminum naphthenate. l l 6.6 ..do 121 20 365v Do. 6.6 do 115 1 345 Do. 6.6 6% commercial aluminum etearate, C., +1% 92 2 357 Do.

naphthenic acid.

l Maintaining the grease composition at 115 F. for an additional 20 hours had negligible edcct on the properties.

In preparing the aluminum soap grease"c 'om positions of this invention, the oil employed is preferably derived from the naphthene base crude las, for example, oils of the Coastal type. 'I'heviscosity of the oil is usually above about 85 seconds Saybolt at 210 F. and preferably from 75 to 220 seconds Saybolt at 210*7 F. 'I'he aluminum soaps are added to the oil at a. temperature of between 280 F. and 300 F. and the mixture heated in the usual type heating kettle to` obtain a urelatively homogeneous mixture. The heating kettle is furnished with close tting' Scrapers for example, small steel -scrapers attached to the outer edge of the sweep and kept at close scraping relation by means of adjusting screws. The particularly close scraping insures thorough mixing of the mass, reduces the formation of a grease composition of lumpy consistency, increases the transfer oi.'l heat into the mass, and thus reduces the time of cooking.

The mass' of aluminum stearate usually eniployed is between 3 and 8% and preferably about 5% by weight of the oil. It is to be understood rthat in this blending aluminum soaps of saturated fatty acids containing between about and carbon atoms in the molecule other than stearic acid, maybe employed and that aluminum stearate is but a preferred compound.` The admixture of the aluminum naphthenate or aluminum oleate ory free fatty acid or naphthenic acids Ain amounts of about 10% by weightof the aluminum stearate overcomes the tendency lof the stearate to set upon cooling to a hard gel and permits the mixture to be cooled iquickly, and the use of any device of suitable form capable of rapidly and uniformly cooling the mixture. Usually in4 incorporating the soap additives into the mineral oil the mixing is made'ilrst with about 10 to 20% of the total quantity of the oil to be used and the mixture lworked into-a thick paste. 'Ihe paste is then stirred into the bal- The mass after heating in the'kettle is then rapidly cooled by passing through any type of cooling equipment capable of rapidly and uniformly cooling the mixture. 'I he cooling is effectedtoa temperature of about the ltransition temperature or even slightly below. Suitable means of cooling the mass are the pan cooling l as in the prior art, or the use of any jacketed equipment in which the isl relatively uniformly cooled. While the grease material is being lcooled to about the transition temperature the mass is agitated. When the temperature of-about transition is 'reached the agitation is discontinued and the mass allowed to cool further in order to permit the desirable change in texture 0f the mixture. O'OCCIH'.

- ness to metallic surfaces. The grease composition may also contain other ingredients as desired.

For example, the viscosity of the grease may be considerably increased by the addition of oil thickeners such'as polymers `of o lens especially loi' the iso-oleilns, and particularly of isobutylene and the-iso-amylenes. 'For this purpose, the

4 polymers having molecular weights of between ance of the oil which .is heated during stirring to a temperature between 280F. and 350' F. and held at that temperature until all the soap is thoroughly incorporated into a smooth, homogeneous mixture. 'I'he aluminum naphthenatev of commerce varies considerably according to its oil content and if it is very well de-oiled, it generally requires a higher temperature in order to bring it into solutiorn In such a caseit is found preferable to add aluminum naphthenate .to the oil and to heat up the mixture to a temperature of between 350 F. and 450 F. while stirringand then to add the aluminum"naphthenate-oil concentrate to the aluminum stearate-oil mixture 30,000 and 200,000 are preferred andv they are ordinarily used in amounts from about 0.05% to 10.25%, depending upon the molecularweight of the Polymer employed. Oxidation inhibitors of various types may be added to the oil as well as facturingwprocess whichshould be read in con #junction with the drawings presented 4in Figure '2. Figure 2 shows a jacketed kettle I0 fitted interl nally with paddles il having scraper terminals i2- which can be nely adjusted to work upon the entire surface of the kettle. V'Ihe motion of thepaddles in the kettle insures very complete and thorough agitation within the kettle. vThe ljacket portion I3 of fthe kettle Ill is adapted for the passing in through line I4 and the passing .out through line I5 of steam either under nor- I8 to make a thick paste.

mal or superatmospheric pressure as temperatures within the. kettle I require.v Under the conditions of such means of agitation and of a temperature between about 280 F. and about 300 F., suillcient oil of suitable character as a` and homogeneous, the mixture is passed from the' bottom of the kettle through line I9 to a screw scraper chiller 20. The chiller 20 has an outer of the cooling water in the jacket. Operation of grease through the chiller was opposite to that of the motion of the screw and to the direction the chiller in this way adds between and 40 p. s. i. to the back pressure. The most satisfactory screw rotation for the particular type Carbondale chiller employed was 150 R. P. M. from the standpoint of cooling efiiciency. The grease was cooled in one pass through this chiller to 95 F. and drawn directly to the containers of the size desired.

The resulting grease had a worked A. S. T. M. penetration of 360, and was exceptionally smooth and transparent, and was highly adhesive. It

jacket 2I 4through which a cooling medium, usually water, passes in through line 22 and out through line 23.95; The screw 24 within the chiller is usually' operatdlcountercurrently to the direction of the ilowfofythe grease from line I9 and countercurrently to the direction of the cooling Aiiuid in the jacket 2l. The scraper screw is operated by the motor 26 through gears 26 and transwithin the mass is reached, agitation within the kettle is discontinuedaand the massis allowed to settle and Ito cool Iurtlrierv until the transition in structure has been satisfactorily eiected. The

gel composition is thenlremoved from thekettle through a T 29 on line I9 and passed tol shipping. containers.

40 In continuous operation it is usual to employ a' series of kettles similarly equipped to that desig- `cooling in the chiller is effected to about thev transition temperature. The cooled grease in such operation is passed directly` through a T 3l on line 28 to the shipping containers wherein,

settling and further cooling to perature are eected.

EXAMPLE I An aluminum stearate grease product was prepared by adding 5.0 parts by weight of aluminum stearate, 0.5 part of aluminum oleate, and 1.0 part of naphthenic acids to about 20 parts of a' atmospheric temnaphthene type lubricating oil which had'an initial viscosity of 160 seconds Saybolt at 210 F. The ingredients were stirred together to a thick paste, all lumps of aluminum stearate being carefully rubbed out. '12.5 parts of the same naphthene type oil as previously used were now added and the mixture heated while stirring to about could be readily dispersed through the usual grease guns available at commercial outlets and was found to ilow under its own weight attemperatures above 30 F.

EXAMPLE II A chassis lubricant was made by adding 3.6 parts by weight of aluminum stearate containing 10% of free fatty acid, 1.0 part of oleic acid and 0.4 part of aluminum naphthenate (the naphthenic acid obtained from Venezuelan gas oil) to about 20 parts of a naphthene lubricating oil which had an initial viscosity of 175 seconds Saybolt at 210 F. The ingredients were stirred together in a thick paste and after thorough incorporation, 74 Vparts of the same lubricating oil pre--4 viously used were added and the mixture was heated while stirring to about 280 F. The stirring continued for about two hours and the mixture was found to be completely homogeneous. While still iiuid,'one part by weight of a 6.0% oil solution of a linear polymer of isobutylene having a -molecular weight of about 40,000-60,000 was added for the purpose of thickening the oil. On cooling, the mixture set into a soft solid body which -was then worked into a smooth, semi-duid grease which was'just soft enough to ow under its own weight at room temperature.

The semi-fluid grease had an A. S. T. M. penetration of 390-400 at 77 F. It was highly adhesive and showed little or no tendency to splatter or to' drop from the shackles or springbolts of an automobile chassis. The composition was readily di'spensable at 0 F. from a grease gun commonly available at commercial grease outlets.

' TheA following table shows the effect of the free 280-300 F. Stirring was continued for approximately one hour or until the mixture was found to be completely homogeneous. One. part-of al 6.0% oil solution of a linear polymer of isobutyiene, the isobutylene vhaving a molecular weight of about 40,090 to 60,000 was added. This material was pumped out of the kettle and through a Carbondale type chiller in which theow of the fatty acid upon the consistency during storage:

A. S. T. M. penetration Grease freshly Alter two ummm prestar maar I e age emite above v Percent As a comparison of the lubricating quality. greases of similar consistency vand of the following compositions were prepared:

vCorn si- Composi- Coni tioxn on B tici???si Aluminum stearato 4. 0 3. 3

Oil solution polybutene Minerallubxicating oil lOver'the free stearic acid already contained lin the aluminum l stearato.

The three greases were tested in crawler-type tractor with the following results: y

Number of days run on test-7. Air temperature25-30 F. Ground frozen.

in the moieeuie, naphthemc acids and their a1u- Composition B Composition A l Composition C i Average temperature of rollers. 150-170 F 12o-150 F ilo-110 F. Number o! roller failures 4 2 0. Tem rature at failure Brass bushings tend to swell against shaft. Shaft blue colored and brass swelled tight against shaft in case of failure.

Rollers filled. i2 oz. in bottom rollers; 3 oz. in top rollers.

The grease could be added only at temperatures above F. and the usual grease gun equipment could not be used because the grease would not flow to the pump. Complete refilling of the upper rollers every day and sometimes 2 times a day was necessary due to the improper feeding ot the grease in the track rollers. Part running hot and the grease rimning out through the seal. This generally necessitated 3 lubrlcations per day.

Con ition of rollers aftertests..

Quantity of lubricant used Average consumption 500+ Same as composition A Same as composition A...

Complete refilling of upper rollers every day. Lower rollers had to b c refilled twice each day. Sometimes necessary to reiubricate rollers 3 times per day when v running very hot.

leakage through seals.

Same as composition A.

1% oz. oi grease every 2 days to upger rollers. 4 oz. of grease gun ad ed every 2l days to bottom rollers.

Noticeable The present invention is not to be limited by any theory of a method of manufacture, or to any particular type of aluminum soaps, but only to the following claims or their equivalents.

We claim:

1. A lubricating grease capable of iiowing under its own weight at normal atmospheric tem-A containing between-10 and 20 carbon atoms in the molecule, naphthenicfacids and their aluminum derivatives as a crystallization inhibitory compound for said aluminum soaps in mineral oil.

2. A lubricating grease according to claim l in which the compound inhibiting the crystallization in mineral oil of the aluminum soap of the fatty acid containing between 10 and 20 carbon atoms in the molecule is an unsaturated fatty acid containing between 10 and 20 carbontatoms in the molecule. n

3. A lubricating grease according to claim 1 in which the compound inhibiting the crystallization in mineral oil of the aluminum soap of the fatty acid containing between 10 `and 20vcarbon atoms in the molecule is a mixture of the alu- ?'minum soap of an'unsaturated fatty acid containing between 10 and 20 carbon atoms in the molecule and an unsaturated fatty acid contaming between 10 and 20 carbon atomsin the molecule.

4. A lubricating grease for the chassis parisof automobiles and crawler-type tractors comprising a viscous naphthenic base lubricating oil compounded in grease forming proportions with about 3% to 8% of an aluminum soap in asaturated fatty acid containing between 10 and 20 carbon atoms in the molecule and not more than 1.5% of an unsubstitutedcarboxylic acid compound of the class consisting of unsaturated fatty acids` containing between about 10 and 20 carbon atoms automobiles and crawler-type tractors comprising a viscous naphthenic base lubricating oi-l compounded in grease forming proportions with about 1 3% to.8% of aluminum stearate and from about 0.25% tol 1.5% of an unsubstituted carboxylic acid compound of the class consisting'of unsaturated fatty acids containing between 10 and 20 carbon atoms in the molecule, naphthenic acids and their aluminum derivatives as a crystallization inhibitory compound for aluminum stearate in said viscous lubricating oil,the same being incorporated so as to form a homogeneous semiuid grease just capable of iiowing under its own weight at room temperature.

6. Alubricating grease for the chassis parts of a crawler-type tractor comprisingl a mineral naphthenic base lubricating oil having a viscosity of from 160 to 180 seconds Saybolt at210 F. compounded in grease forming proportions with about 3% to 8% of aluminum stearate, about 0.25% to 1.5% of an unsubstituted carboxylic acid compound of the class consisting of unsaturated fatty acids containing between A10 and 20 carbon atoms 'in the molecule, naphthenic acids and their aluminum derivatives as a crystallization inhibitory compound for said quantity of aluminum stearate in said mineral lubricating oil, the same being worked into a homogeneous semi-fluid grease havinga penetration of between 300 and 400 at '7. A lubricating grease for the chassis parts ofV crawler-type tractors according to claim 6 in which the compound inhibiting the crystallizationdnmineral oil of the aluminum stearate is "oleic acid.

8. A senil-fluid lubricating grease for the chassis parts of crawler-type tractors comprising' a mineral naphthenic base lubricating oil of from to 200 seconds Saybolt at 210 F., about 5% of aluminum stearato, about 0.5% of a petroleum naphthenic acid and about 0.1% of polyisobutylene as a thickener, the whole :being worked into a semi-fluid grease having a penetration of between 300 to 400 at 77 F. and just capable of owing under its own weight at room temperature.

9. A lubricating grease for machinery operating under conditions ofv local high temperature increase, of irregular and shock load effects and of frictional 4forces beyond the nlm strength of Like original-well lubricated.

lization inhibitory compound for said aluminum soap in the mineral oil.

10. A lubricating grease for the chassis parts of a crawler-type tractor comprising a mineral naphthenic base lubricating oil having a viscosity 1o oi from 160 to 180 seconds Saybolt at 210 F. compounded in grease-forming proportions with about 3 to 8% oi' aluminum stearato, about 0.25 to 1,5% o1 a petroleum naphthenic acid as a crystallization inhibiting compound for said quantity of aluminum stearato in said lubricating oil, the same being worked into a homogeneous semi-fluid grease having a penetration of between 300 and 400 at '17 F.

JOHN C..ZIMMER.

ARNOLD J. MORWAY. 

